A very simple, green and efficient protocol is developed in which zinc chloride-exchanged K10-montmorillonite (clayzic) is employed as a Lewis acid catalyst in aqueous media at room temperature for the synthesis of various benzimidazoles and quinoxalines from carbonyl compounds and o-phenylenediamine. Among the various catalysts (including claycop and Zn 2+ –Y) studied, clayzic produces benzimidazoles and quinoxalines in higher yield, and with a flexible diamine such as ethylenediamine only the bis-Schiff base is formed. Other salient features of this protocol include milder conditions, atom-economy, absence of coupling agents, and no wastes.